Manganese‐Catalyzed Hydrogen‐Autotransfer C−C Bond Formation: α‐Alkylation of Ketones with Primary Alcohols

Peña‐López, Miguel; Piehl, Patrick; Elangovan, Saravanakumar; Neumann, Helfried; Beller, Matthias

doi:10.1002/anie.201607072

Cited by 293 publications

(157 citation statements)

References 74 publications

(19 reference statements)

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“…[56] The complexity of the transition states generated during some transition-metal mediated transformations makes enantiocontrol difficult, but some preliminary studies show promise (enantioselectivities are currently moderate), [57] and a recently developed H- borrowing strategy (H-auto-transfer) could have potential for modification to an asymmetric system. [58] Other interesting alternatives to solve this problem is the kinetically controlled enantioselective α-protonation of α-branched ketones. [59] Although many examples have been reported to date, a highly efficient system with a broad scope is still unknown.…”

Section: Discussionmentioning

confidence: 99%

Direct Asymmetric Alkylation of Ketones: Still Unconquered

2017

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The alkylation of ketones is taught at basic undergraduate level. In many cases this transformation leads to the formation of a new stereogenic center. However, the apparent simplicity of the transformation is belied by a number of problems. So much so, that a general method for the direct asymmetric alkylation of ketones remains an unmet target. Despite the advancement of organocatalysis and transition-metal catalysis, neither field has provided an adequate solution. Indeed, even use of an efficient and general stoichiometric chiral reagent has yet to be reported. Herein we describe the state-of-the-art in terms of direct alkylation reactions of some carbonyl groups. We outline the limited progress that has been made with ketones, and potential routes towards ultimately achieving a widely applicable methodology for the asymmetric alkylation of ketones.

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Section: Discussionmentioning

confidence: 99%

Direct Asymmetric Alkylation of Ketones: Still Unconquered

2017

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“…Another kind of C-C bond formation was published by our group in a report of α-alkylation of ketones with primary alcohols through a hydrogen autotransfer reaction (hydrogen borrowing). [38] Catalyst 10a was found to be optimal out of the tested systems 10a, 10b and 10d (Figure 7).…”

Section: C-c Bond Formationmentioning

confidence: 99%

Homogeneous Catalysis by Manganese‐Based Pincer Complexes

2017

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Base‐metal catalysis, especially with non‐noble‐metal pincer‐type catalysts, is increasingly used in organic synthesis and thus becoming more and more important for organometallic chemistry. After ruthenium‐, iridium‐ and iron‐based pincer‐type complexes became established as state‐of‐the‐art catalysts for (de)hydrogenation reactions in the past decade, manganese complexes have most recently been successfully applied in related transformations. Specifically, this microreview covers their recent progress in (de)hydrogenation and transfer (de)hydrogenation as well as in C–C and C–X bond‐forming reactions.

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“…Among these elements, manganese is the main topic of numerous publications devoted to tandem oxidation, mainly Mn(III) and Mn(IV) . For instance, manganese has recently attracted wide interest for multicomponent reactions based on pincer‐type manganese complexes …”

Section: Reactivity Of Eco‐mn Catalystsmentioning

confidence: 99%

“…[95][96][97][98] For instance, manganese has recently attracted wide interest for multicomponent reactions based on pincer-type manganese complexes. [99][100][101][102][103][104][105][106] Eco-Mn LA and Eco-Mn Ox catalysts possess a polymetallic composition which combines metal transition elements with Lewis or Brønsted acidity properties (Mn, Fe, Al) and oxidative properties (Mn, Fe). Eco-Mn LA and Eco-Mn Ox catalysts were studied in sequential tandem oxidation as a "Janus catalyst", which is an eco-material with two different but concomitant catalytic properties.…”

Section: Tandem Sequential Oxidation Catalyzed By Eco-mn La Andmentioning

confidence: 99%

Eco‐Mn Ecocatalysts: Toolbox for Sustainable and Green Lewis Acid Catalysis and Oxidation Reactions

et al. 2020

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Phytoextraction is one of the most promising phytotechnologies used to restore natural environments degraded by mining activities. In New Caledonia, a few plant species, which belong to the Grevillea genus, have the ability to extract Mn from soil and accumulate it in abundance (over 1 % of leaves dry weight). This review describes the use of Grevillea Mn‐accumulating plant species to produce the first bio‐sourced Mn catalysts, called Eco‐Mn catalysts. Extensive structural studies of Eco‐Mn catalysts have highlighted an original composition characteristic of their vegetal origin. Eco‐Mn catalysts have demonstrated competitive catalytic activities compared to conventional Mn catalysts in Lewis acid catalysis, aminoreductions, alcohol oxidations, epoxidation reactions, oxidative cleavage of 1,2‐diols and alkenes and “Janus catalysts” for sequential tandem oxidations such as tandem carbonyl‐ene cyclisation, synthesis of substituted pyridines and oxidative iodination of ketones.

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Manganese‐Catalyzed Hydrogen‐Autotransfer C−C Bond Formation: α‐Alkylation of Ketones with Primary Alcohols

Cited by 293 publications

References 74 publications

Direct Asymmetric Alkylation of Ketones: Still Unconquered

Direct Asymmetric Alkylation of Ketones: Still Unconquered

Homogeneous Catalysis by Manganese‐Based Pincer Complexes

Eco‐Mn Ecocatalysts: Toolbox for Sustainable and Green Lewis Acid Catalysis and Oxidation Reactions

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